Reaction of potassium dichromate with gamma-glutamylcysteine, N-acetylcysteine, and cysteine in aqueous solution resulted in the formation of 1:1 complexes of Cr(VI) with the cysteinyl thiolate ligand. The brownish red Cr(VI)-amino acid/peptide complexes exhibited differential stability in aqueous solutions at 4 degrees C and ionic strength = 1.5 M, decreasing in stability in the order: gamma-glutamylcysteine > N-acetylcysteine > cysteine. (1)H, (13)C, and (17)O NMR studies showed that the amino acids act as monodentate ligands and bind to Cr(VI) through the cysteinyl thiolate group, forming RS-Cr(VI)O(3)(-) complexes. No evidence was obtained for involvement of any other possible ligating groups, e.g., amine or carboxylate, of the amino acid/peptide in binding to Cr(VI). EPR studies showed that chromium(V) species at g = 1.973-4 were formed upon reaction of potassium dichromate with gamma-glutamylcysteine and N-acetylcysteine. Reaction of potassium dichromate or sodium dichromate with N-acetylcysteine and the methyl ester of N-acetylcysteine in N,N-dimethylformamide (DMF) also led to the formation of RS-Cr(VI)O(3)(-) complexes as determined by UV/vis, IR, and (1)H NMR spectroscopy. Thus, an early step in the reaction of Cr(VI) with cysteine and cysteine derviatives in aqueous and DMF solutions involves the formation of RS-CrO(3)(-) complexes. The Cr(VI)-thiolate complexes are more stable in DMF than in aqueous solution, and their stability towards reduction in aqueous solution follows the order cysteine < N-acetylcysteine < gamma-glutamylcysteine < glutathione.

SynopsisT h e diffusivities of simple gases through a series of polyurethane block copolymers of differing aromatic urethane content and type of soft segment were measured using a quadrapole mass spectrometer as a detecting device. Although an Arrhenius expression generally described the temperature dependence of diffusion in this system, a discontinuity was observed in the Arrhenius plots for some materials, and the discontinuity was found to be related to the onset of the glass transition in the hard domains. Increasing the hard segment content of the materials decreased the diffusivity due to the increase in the activation energy of diffusion. Increasing the soft segment length brought about a decrease in the activation energy with an increase in diffusivity. Polyester urethanes had lower activation energies for diffusion than polyether urethanes of similar hard segment composition. Finally, as the penetrant diameter was increased, a decrease in the diffusivity and an increase in the activation energy was noted.